CN104941653B - A kind of copper and tin composite oxide catalysts and its production and use - Google Patents
A kind of copper and tin composite oxide catalysts and its production and use Download PDFInfo
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Abstract
The invention provides a kind of copper and tin composite oxide catalysts and its production and use, the weight/mass percentage composition that the copper and tin composite oxide catalysts are accounted for by each component mainly includes 99.00~99.98% CuO；0.02~1.00% SnO2, the CuO and SnO2Weight/mass percentage composition sum be 100%.The copper and tin composite oxide catalysts uniformity is higher, the big (80~100m of specific surface area2/ g), M2 selectivity >=90.0% in M2 monomer reactions is synthesized for " direct method ", silicon power raw material conversion ratio >=66.0%, and the preparation method of the copper and tin composite oxide catalysts is wet chemistry method, it is simple to operate, easy control of reaction conditions, favorable reproducibility, production cost is relatively low, is adapted to industrial mass production.
Description
Technical field
The invention belongs to catalyst technical field, is related to a kind of copper and tin composite oxide catalysts and preparation method thereof and uses
On the way, more particularly to a kind of it is used to synthesize laminar copper and tin composite oxide catalysts and its preparation side of dimethyldichlorosilane
Method.
Background technology
Organosilicon material refers to a kind of high molecular polymer containing Si-C chemical combination keys, because it has resistance to low high temperature, resistance to old
Change, electric insulation, the corrosion-resistant and excellent specific property such as nonpoisonous and tasteless, it is widely used in electronics, automobile, oil, chemical industry, builds
Build, the field such as Aero-Space.Methylchlorosilane has become organosilicon as the most important monomer material of synthesizing organo-silicon product
The basis of industry and pillar.Wherein, with dimethyldichlorosilane [(CH3)2SiCl2, abbreviation M2] have the call, about occupy
The 90% of machine silicon industry monomer yield, its production technology and level are to determine the key of silicone industry.
Nineteen forty-one is industrially generally used to be invented by GE Luo Qiao (E.G.Rochow) at present " direct
Method " synthesizes M2 monomers, i.e., under copper-based catalysts effect, direct substitution reaction occurs by silica flour (Si) and chloromethanes (MeCl),
Course of reaction is as shown in Figure 1.While synthesizing M2 using " direct method ", due to the crowds such as disproportionation, thermal decomposition, hydrolysis adjoint can occur
More complicated side reaction, causes accessory substance more, including M1, M3, M1H, M2H, low-boiling-point substance and high-boiling components, causes economic benefit to drop
It is low.Therefore, M2 yield and the study hotspot of selectivity always various countries' silicone industry are improved.With process conditions and reaction
Device is continued to optimize, and developing new and effective catalyst system turns into the key for realizing the target.
It is well known that Cu base catalysis materials are to be currently known to be catalyzed maximally effective catalyst to " direct method ".Add auxiliary agent
Zn, Sn or its oxide, because they and major catalyst have mutually synergy, moved so as to cause the diffusion of Cu bases catalyst
Move property improvement, can further improve M2 selectivity (J.Catal.1991,128,468-478；US Patent 4500724,
1985.).It is mainly higher from external import, production cost to synthesize catalyst used in the monomer for silicone industry in China industry at present.
In view of monomer M2 purposes is wide, demand is big, price is high, the small raising of copper catalyst performance will all produce huge economic effect
Benefit；Therefore, the development of domestic copper-based catalysts of cheap, excellent quality, stable performance is organosilicon industry difficulty urgently to be resolved hurrily
Topic.
Industrial initially use electrolytic copper powder specific surface area is smaller, causes poor catalytic activity；The protochloride of later development
Copper self stability is poor, and can produce silicon tetrachloride in reacting, and it easily forms azeotropic mixture with trim,ethylchlorosilane, makes first
The refined of base chlorosilane becomes particularly difficult, therefore is gradually eliminated.Most commonly used in methylchlorosilane production at present is three
First copper catalyst Cu-Cu2O-CuO, the catalyst have the advantages that M2 selectivity is high, stability is good and easily stored.
U.S. SCM (Smith Corona Marchant) company reports passes through air oxidation and high energy ball using copper powder
Grind polynary copper Cu-Cu prepared by two-step process2O-CuO catalyst, " direct method " synthesis M2 is carried out with it, is achieved excellent
Catalytic performance, silica flour conversion ratio and M2 selectivity are all higher；Domestic Inst. of Jilin Chemical Industry Co the Ministry of Chemical Industry (CN
1072870 A) and Chengdu organosilicon research center (CN1008423 B) etc. certain research also has been carried out to polynary copper catalyst,
But its M2 selectivity and catalytic activity are obvious relative to the catalyst gap of SCM Corporation of the U.S., and product quality is also unstable；CN
104138760 A disclose one kind and contain tin promoter, as organic silicon monomer synthetic reaction, preferably dimethyldichlorosilane
Co-catalyst in synthetic reaction cupper-based catalyst system, the carrier containing tin promoter are metallic copper and/or Cu oxide
During powder, such as Cu, CuO, Cu2O, Cu-CuO, Cu-Cu2O, CuO-Cu2O, Cu-Cu2During O-CuO, described one kind contains tin promoter
In：Cu (5~99.0%), Cu2O (0.05~90.0%), CuO (0.05~85.0%), simple substance Sn and/or the alloy containing Sn
And/or the compound 0.05~90.0% containing Sn.
At present both at home and abroad the copper-based catalysts of Patents and document report mainly using chemical dry (including solid-phase ball milling
Method and gaseous oxidation reducing process) prepare, these method complex process, required equipment is expensive, high energy consumption, and catalyst component lacks can
Control property.
Copper-based catalysts for " direct method " synthesis M2 monomer reactions need further to study, further to improve
M2 selectivity and silicon power raw material conversion ratio.
The content of the invention
It is an object of the invention to provide a kind of copper and tin composite oxide catalysts and its production and use, the copper
Tin composite oxide catalysts uniformity is higher, the big (80~100m of specific surface area2/ g), it is anti-for " direct method " synthesis M2 monomers
M2 selectivity >=90.0%, silicon power raw material conversion ratio >=66.0% in answering.
To use following technical scheme up to this purpose, the present invention：
An object of the present invention is to provide a kind of copper and tin composite oxide catalysts, and the copper and tin composite oxides are urged
The weight/mass percentage composition that agent is accounted for by each component mainly includes following component：
CuO 99.00~99.98%
SnO20.02~1.00%
The weight/mass percentage composition sum of each component is 100%.
Copper and tin composite oxide catalysts provided by the invention mainly include CuO, in addition to micro SnO2, specifically,
In the copper and tin composite oxide catalysts CuO weight/mass percentage composition be 99.00~99.98%, such as 99.05%, 99.1%,
99.2%th, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9% or 99.95% etc.；SnO2Quality
Percentage composition be 0.02~1.00%, such as 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%,
0.8%th, 0.9% or 0.95% etc..
As SnO in copper and tin composite oxide catalysts2Content be less than 0.02% when, catalyst activity it is not high, M2 choosing
Selecting property≤75.0%, silicon power raw material conversion ratio≤40.0%；As SnO in copper and tin composite oxide catalysts2Content be more than 1%
When, the activity of catalyst is obvious to be reduced, M2 selectivity≤20.0%, silicon power raw material conversion ratio≤10.0%.When the copper and tin is answered
The content for closing CuO in oxide catalyst is less than 99.0% and SnO2Content at 0.02~1%, the activity decrease of catalyst
Substantially, M2 selectivity≤40.0%, silicon power raw material conversion ratio≤30.0%.
As preferable technical scheme, the copper and tin composite oxide catalysts by the weight/mass percentage composition that each component accounts for by
Following component composition：
CuO 99.00~99.98%
SnO20.02~1.00%
The weight/mass percentage composition sum of each component is 100%.
Preferably, SnO in the copper and tin composite oxide catalysts2Be dispersed in CuO, the inside of the CuO and
Surface is distributed with SnO2。
Preferably, the specific surface area of the copper and tin composite oxide catalysts is 80~100m2/ g, such as 82m2/g、85m2/
g、87m2/g、90m2/g、92m2/g、95m2/ g or 98m2/ g etc..
The component of copper and tin composite oxide catalysts provided by the invention is homogeneous, is acted synergistically between component strong；And have
Larger specific surface area, up to 80~100m2/ g so that the contact probability between component and silica flour is effectively increased, being capable of shape
Into more Cu3Si activity phases, so as to improve M2 selectivity and silica flour conversion ratio.
The copper and tin composite oxide catalysts are sheet.
Preferably, the thickness of the sheet copper and tin composite oxide catalysts is 50~60nm, as 50nm, 52nm, 53nm,
55nm, 56nm, 57nm, 59nm or 60nm etc..
The second object of the present invention is to provide a kind of preparation method of copper and tin composite oxide catalysts, the preparation side
Method is：Alkali lye is mixed with the solution containing copper ion and tin ion, hydro-thermal reaction is carried out after aging in a kettle, obtains copper
Tin composite oxide catalysts.
The present invention prepares copper and tin composite oxide catalysts using wet chemistry method, and operating method is simple, accurately controls
The composition of catalyst, the component uniformity of obtained catalyst is higher, and industrial production cost is relatively low.
After methods described also terminates including hydro-thermal reaction, obtained product is subjected to separation of solid and liquid, and will be isolated
Solid washs, and dries.The mode of the separation of solid and liquid is without specifically limited, as long as can reach the purpose by solid and liquid separation
, typical but non-limiting solid-liquid separation method has：Centrifugation or filtering etc..
Preferably, in the solution containing copper ion and tin ion the mol ratio of copper ion and tin ion be 1500~
2000:1, such as 1550:1、1600:1、1700:1、1800:1、1850:1、1900:1 or 1950:1 etc..
Preferably, the concentration of copper ion is 0.26~1.56mol/L in the solution containing copper ion and tin ion, such as
0.35mol/L、0.45mol/L、0.55mol/L、0.85mol/L、1.05mol/L、1.15mol/L、1.20mol/L、
1.35mol/L, 1.46mol/L or 1.55mol/L etc..
Preferably, the volume ratio of the alkali lye and the solution containing copper ion and tin ion is 1:3~2:1, such as 1:
2、1:1、2:3、4:3、5:3 or 2:1 etc..
Preferably, the concentration of the alkali lye is 0.1~2mol/L, as 0.2mol/L, 0.3mol/L, 0.5mol/L,
0.6mol/L, 0.8mol/L, 1.0mol/L, 1.2mol/L, 1.5mol/L, 1.7mol/L or 1.9mol/L etc..The alkali lye
Concentration refer to alkali lye mixed with the solution containing copper ion, tin ion before concentration.
The temperature of the aging is 0~10 DEG C, such as 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C, 7 DEG C, 8 DEG C or 9 DEG C.
Preferably, the time of the aging is 4~24h, such as 5h, 6h, 8h, 10h, 12h, 15h, 17h, 20h, 22h or 23h
Deng.
Ageing process is advantageous to the formation of nucleus, shortens follow-up crystallization time.
Preferably, the reaction temperature of the hydro-thermal reaction be 100~180 DEG C, such as 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C,
150 DEG C, 160 DEG C, 165 DEG C or 175 DEG C etc..
Preferably, the reaction time of the hydro-thermal reaction is 12~24h, such as 13h, 14h, 15h, 18h, 20h, 22h, 23h
Or 23.5h etc..
Preferably, the reactor is autoclave, and the autoclave is the reaction under high pressure that chemical field is commonly used
Device.
Preferably, the volume of the autoclave is 200~1000mL, as 300mL, 400mL, 500mL, 600mL,
800mL or 900mL etc..
Preferably, the liner of the autoclave is polytetrafluoroethylene (PTFE).
The copper ion source is in soluble copper salt.
Preferably, the soluble copper salt is any of copper sulphate, copper nitrate, copper chloride or copper acetate or at least two
The combination of kind, typical but non-limiting combination is such as：Copper sulphate and copper nitrate, copper chloride and copper acetate, copper sulphate, copper nitrate with
Copper chloride, copper sulphate, copper nitrate, copper chloride and copper acetate etc..
Preferably, the tin ion derives from soluble pink salt.
Preferably, the soluble pink salt is any of nitric acid tin, stannic chloride or tin acetate or at least two group
Close, typical but non-limiting combination is such as：Nitric acid tin and stannic chloride, stannic chloride and tin acetate, nitric acid tin, stannic chloride and tin acetate
Deng.
Preferably, the alkali lye is any or extremely in sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor or urea liquid
Few two kinds mixed liquor, typical but non-limiting mixed liquor is such as：Sodium hydroxide solution and potassium hydroxide solution, ammoniacal liquor and urea
Solution, sodium hydroxide solution, potassium hydroxide solution and ammoniacal liquor, potassium hydroxide solution, ammoniacal liquor and urea liquid, sodium hydroxide are molten
Liquid, potassium hydroxide solution, ammoniacal liquor and urea liquid etc..
Preferably, the solvent of the alkali lye is water and/or ethanol；The solvent of the solution containing copper ion and tin ion
For water and/or ethanol.
It is described to be blended in 20~40 DEG C of progress, such as at 22 DEG C, 25 DEG C, 26 DEG C, 28 DEG C, 30 DEG C, 32 DEG C, 35 DEG C, 37 DEG C or
39 DEG C etc..
Preferably, it is stirred in the mixed process.
Preferably, the temperature of the drying be 60~200 DEG C, such as 65 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 120 DEG C,
150 DEG C, 170 DEG C, 180 DEG C or 190 DEG C etc..
Preferably, the time of the drying is 4~24h, such as 5h, 6h, 8h, 10h, 12h, 15h, 17h, 20h, 22h or 23h
Deng.
As preferable technical scheme, the invention provides a kind of preparation side of the copper and tin composite oxide catalysts
Method, the preparation method comprise the following steps：
(1) at normal temperatures, by 0.1~2mol/L alkali lye be added to containing copper ion with and the solution of tin ion in, copper
The mol ratio of ion and tin ion is 1500~2000:1, the volume ratio of alkali lye and the solution containing copper ion and tin ion
For 1:3~2:1, obtain mixed liquor；
(2) by mixed liquor in 0~10 DEG C of 4~24h of aging；
(3) mixed liquor after aging is transferred in reactor, 12~24h of hydro-thermal reaction is carried out at 100~180 DEG C, it
Separation of solid and liquid afterwards, gained solid washing, dries, obtains copper and tin composite oxide catalysts.
The third object of the present invention is to provide a kind of purposes of described copper and tin composite oxide catalysts, and it is used to have
In machine silicon monomer synthetic reaction, promote the selectivity synthesis of dimethyldichlorosilane.
Compared with prior art, beneficial effects of the present invention are：
1st, copper and tin composite oxide catalysts provided by the invention are only 50~60nm in flake, thickness, specific surface area
Up to 80~100m2/ g, pattern is homogeneous, SnO2It is dispersed preferable.
2nd, copper and tin composite oxide catalysts provided by the invention are used in " direct method " synthesis M2 monomer reactions, with industry
CuO、SnO2, CuO and SnO2Mechanical mixture sample, prepare single CuO and SnO2And commercial catalysts are compared, have more
High M2 selectivity and silicon power raw material conversion ratio, M2 selectivity >=90.0%, silicon power raw material conversion ratio >=66.0%.
3rd, the present invention prepares copper and tin composite oxide catalysts using wet chemistry so that copper and tin composite oxide catalysts
Chemical composition accurately control, and raw material is cheap and easy to get, and product uniformity is higher, simple to operate, without high temperature and calcining
Deng pre-treatment, can be prepared in lower temperature, so as to reduce energy consumption and reaction cost, easy control of reaction conditions, reappear
Property it is good, industrial production cost is relatively low, be adapted to industrial mass production.
Brief description of the drawings
Fig. 1 is the reaction equation that direct substitution reaction occurs for silica flour and chloromethanes.
Fig. 2 is the XRD of copper and tin composite oxide catalysts made from embodiment 1.
Fig. 3 is the SEM figures of copper and tin composite oxide catalysts made from embodiment 1.
Fig. 4 is the grain size distribution of copper and tin composite oxide catalysts made from embodiment 1.
Fig. 5 is the N of copper and tin composite oxide catalysts made from embodiment 12Adsorption/desorption curve.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Raw material and experimental facilities those skilled in the art as described below is commercially available.Wherein, autoclave by
The crack Ze Xiang laboratory apparatus Co., Ltd in Beijing provides.
Embodiment 1：
The preparation method of copper and tin composite oxide catalyst is：
(1) at 20 DEG C, 100mL 0.1mol/L sodium hydroxide solution is added to 50mL and is dissolved with 9.96g in advance
CuSO4·5H2O and 0.01g SnCl4·5H2O(mol(Cu):Mol (Sn)=1500:1) in the aqueous solution, it is stirred until homogeneous,
Obtain mixed liquor；
(2) by mixed liquor in 0 DEG C of aging 4h；
(3) mixed liquor after aging is transferred in the 200mL autoclave of polytetrafluoroethyllining lining, the water at 130 DEG C
After thermal response 18h, 20 DEG C are naturally cooled to, filtering, gained solid is washed for several times, afterwards repeatedly with deionized water and absolute ethyl alcohol
24h is dried at 60 DEG C, obtains copper and tin composite oxide catalysts.
X ' the Pert that obtained copper and tin composite oxide catalysts are produced in Dutch Panalytical companies (PANalytical)
XRD tests are carried out on PRO MPD type Multi-functional X ray diffractometers；Electricity is scanned in the JSM-7001F types of Japanese JEOL companies production
The microscopic appearance of catalyst is observed on sub- microscope；On the BT-9300Z laser particle analyzers of Dandong particle size analyzer Co., Ltd production
Analyze sample granularity distribution；N is tested on the BET specific surface instruments (Novae series) of Kang Ta companies of U.S. production2Adsorption/desorption is bent
Line；ICP tests are carried out on U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers.
Test result：
Fig. 2 is the XRD of obtained copper and tin composite oxide catalysts, wherein, " ◆ " represents CuO characteristic diffraction peak,
SnO2Fail to detect because content is too low；Fig. 3 is the SEM figures of obtained copper and tin composite oxide catalysts, can be with from figure
Find out, obtained copper and tin composite oxide catalysts are in flake, and radial dimension is about 1 μm, and thickness is about 50nm；Fig. 4 is system
Copper and tin composite oxide catalysts particle size distribution figure, as can be seen from the figure obtained copper and tin composite oxide catalysts
Particle diameter all less than 15 μm, most of particle diameter be 3.5 μm；Fig. 5 is the N of obtained copper and tin composite oxide catalysts2Absorption
Desorption curve, it can be seen that the specific surface area of obtained copper and tin composite oxide catalysts can reach 80m2/g；
ICP test results show that copper coin cellulose content is 79.2%, and tin element content is 0.79%.
Embodiment 2：
The preparation method of copper and tin composite oxide catalyst is：
(1) at 25 DEG C, 100mL 2mol/L potassium hydroxide solution is added to 60mL and is dissolved with 12.48g in advance
CuSO4·5H2O and 0.01g Sn (NO3)4(mol(Cu):Mol (Sn)=1879.7:1) in the aqueous solution, it is stirred until homogeneous, obtains
To mixed liquor；
(2) by mixed liquor in 5 DEG C of aging 12h；
(3) mixed liquor after aging is transferred in the 200mL autoclave of polytetrafluoroethyllining lining, in 100 DEG C of conditions
Lower progress hydro-thermal reaction 24h, after naturally cooling to 20 DEG C, filtering, gained solid is washed repeatedly with deionized water and absolute ethyl alcohol
Wash for several times, 20h is dried at 80 DEG C, obtains copper and tin composite oxide catalysts.
Obtained copper and tin composite oxide catalysts are shown in the JSM-7001F type scanning electrons that Japanese JEOL companies produce
The microscopic appearance of catalyst is observed on micro mirror；N is tested on the BET specific surface instruments (Novae series) of Kang Ta companies of U.S. production2
Adsorption/desorption curve；ICP tests are carried out on U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers.
Test result shows that obtained copper and tin composite oxide catalysts are in flake, and radial dimension is about 1 μm, thickness
About 60nm；The specific surface area of copper and tin composite oxide catalysts reaches 90m2/g；Copper in copper and tin composite oxide catalysts
Content is 79.8%, and tin element content is 0.04%.
Embodiment 3：
The preparation method of copper and tin composite oxide catalyst is：
(1) at 30 DEG C, 100mL 1mol/L ammoniacal liquor is added to 50mL and is dissolved with 13.28g CuSO in advance4·5H2O
With 0.01g SnCl4·5H2O(mol(Cu):Mol (Sn)=2000:1) in ethanol solution, stir to being well mixed, mixed
Close liquid；
(2) by mixed liquor in 10 DEG C of aging 24h；
(3) mixed liquor after aging is transferred in the 200mL autoclave of polytetrafluoroethyllining lining, entered at 130 DEG C
Water-filling thermal response 18h, after naturally cooling to 20 DEG C, filtering, gained solid is washed for several times repeatedly with deionized water and absolute ethyl alcohol,
16h is dried at 100 DEG C, obtains copper and tin composite oxide catalysts.
BET specific surface instruments (the Novae systems that obtained copper and tin composite oxide catalysts are produced in Kang Ta companies of the U.S.
Row) on test N2Adsorption/desorption curve；Carried out on U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
ICP is tested.
Test result shows that the specific surface area of obtained copper and tin composite oxide catalysts reaches 100m2/g；Copper and tin composite oxygen
Copper coin cellulose content is 79.98% in compound catalyst, and tin element content is 0.016%.
Embodiment 4：
The preparation method of copper and tin composite oxide catalyst is：
(1) at 35 DEG C, 100mL 0.5mol/L urea liquid is added to 100mL and is dissolved with 15.65g Cu in advance
(NO3)2·3H2O and 0.01g Sn (CH3COO)4(mol(Cu):Mol (Sn)=1600:1) in the aqueous solution, it is stirred until homogeneous,
Obtain mixed liquor；
(2) by mixed liquor in 4 DEG C of aging 12h；
(3) mixed liquor after aging is transferred in the 250mL autoclave of polytetrafluoroethyllining lining, entered at 150 DEG C
Water-filling thermal response 16h, after naturally cooling to 20 DEG C, centrifugation, gained solid is washed for several times repeatedly with deionized water and absolute ethyl alcohol,
12h is dried at 140 DEG C, obtains copper and tin composite oxide catalysts.
By obtained copper and tin composite oxide catalysts in U.S. Pekin-Elmer inductively coupled plasma atomic emissions
ICP tests are carried out on spectrometer.
Test result shows that copper coin cellulose content is 79.3% in obtained copper and tin composite oxide catalysts, and tin element contains
Measure as 0.75%.
Embodiment 5：
The preparation method of copper and tin composite oxide catalyst is：
(1) at 40 DEG C, 100mL 0.5mol/L sodium hydroxide solution is added to 150mL and is dissolved with 15.1g in advance
CuCl2·2H2O and 0.01g SnCl4·5H2O(mol(Cu):Mol (Sn)=1700:1) in solution, solvent is second alcohol and water
Mixed liquor, be stirred until homogeneous, obtain mixed liquor；
(2) by mixed liquor in 4 DEG C of aging 12h；
(3) mixed liquor after aging is transferred in the 500mL autoclave of polytetrafluoroethyllining lining, entered at 180 DEG C
Water-filling thermal response 12h, after naturally cooling to 20 DEG C, filtering, gained solid is washed for several times repeatedly with deionized water and absolute ethyl alcohol,
10h is dried at 160 DEG C, obtains copper and tin composite oxide catalysts.
By obtained copper and tin composite oxide catalysts in U.S. Pekin-Elmer inductively coupled plasma atomic emissions
ICP tests are carried out on spectrometer.
Test result shows that copper coin cellulose content is 79.5% in obtained copper and tin composite oxide catalysts, and tin element contains
Measure as 0.45%.
Embodiment 6：
The preparation method of copper and tin composite oxide catalyst is：
(1) at 20 DEG C, 100mL 0.8mol/L sodium hydroxide solution is added to 300mL and is dissolved with 18.73g in advance
Cu(CH3COO)2·H2O and 0.01g SnCl4·5H2O(mol(Cu):Mol (Sn)=1800:1) in the aqueous solution, stir to equal
It is even, obtain mixed liquor；
(2) by mixed liquor in 4 DEG C of aging 12h；
(3) mixed liquor after aging is transferred in the 1000mL autoclave of polytetrafluoroethyllining lining, entered at 130 DEG C
Water-filling thermal response 18h, after naturally cooling to 20 DEG C, centrifugation, gained solid is washed for several times repeatedly with deionized water and absolute ethyl alcohol,
6h is dried at 180 DEG C, obtains copper and tin composite oxide catalysts.
By obtained copper and tin composite oxide catalysts in U.S. Pekin-Elmer inductively coupled plasma atomic emissions
ICP tests are carried out on spectrometer.
Test result shows that copper coin cellulose content is 79.7% in obtained copper and tin composite oxide catalysts, and tin element contains
Measure as 0.1%.
Embodiment 7：
The preparation method of copper and tin composite oxide catalyst is：
(1) at 20 DEG C, 100mL 1mol/L sodium hydroxide solution is added to 60mL and is dissolved with 6.31g in advance
CuSO4·5H2O、9.89g Cu(CH3COO)2·H2O and 0.01g SnCl4·5H2O(mol(Cu):Mol (Sn)=1900:1)
Ethanol solution in, be stirred until homogeneous, obtain mixed liquor；
(2) by mixed liquor in 4 DEG C of aging 12h；
(3) mixed liquor after aging is transferred in the 200mL autoclave of polytetrafluoroethyllining lining, entered at 130 DEG C
Water-filling thermal response 18h, after naturally cooling to 20 DEG C, centrifugation, gained solid is washed for several times repeatedly with deionized water and absolute ethyl alcohol,
4h is dried at 200 DEG C, obtains copper and tin composite oxide catalysts.
By obtained copper and tin composite oxide catalysts in U.S. Pekin-Elmer inductively coupled plasma atomic emissions
ICP tests are carried out on spectrometer.
Test result shows that copper coin cellulose content is 79.9% in obtained copper and tin composite oxide catalysts, and tin element contains
Measure as 0.02%.
Comparative example 1：
The preparation method of CuO catalyst is：
(1) at 20 DEG C, 100mL 0.1mol/L sodium hydroxide solution is added to 50mL and is dissolved with 9.96g in advance
CuSO4·5H2In the O aqueous solution, it is stirred until homogeneous, obtains mixed liquor；
(2) by mixed liquor in 0 DEG C of aging 4h；
(3) mixed liquor after aging is transferred in the 200mL autoclave of polytetrafluoroethyllining lining, entered at 130 DEG C
Water-filling thermal response 18h, after naturally cooling to 20 DEG C, filtering, gained solid is washed for several times repeatedly with deionized water and absolute ethyl alcohol,
18h is dried at 60 DEG C, obtains single CuO catalyst.
Obtained CuO catalyst is enterprising in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Row ICP is tested.
Test result shows that copper coin cellulose content is 79.8% in obtained CuO catalyst.
Comparative example 2：
SnO2The preparation method of catalyst is：
(1) at 20 DEG C, 100mL 0.1mol/L sodium hydroxide solution is added to 50mL and is dissolved with 0.01g in advance
SnCl4·5H2In the O aqueous solution, it is stirred until homogeneous, obtains mixed liquor；
(2) by mixed liquor in 0 DEG C of aging 4h；
(3) mixed liquor after aging is transferred in the 200mL autoclave of polytetrafluoroethyllining lining, entered at 130 DEG C
Water-filling thermal response 18h, after naturally cooling to 20 DEG C, filtering, gained solid is washed for several times repeatedly with deionized water and absolute ethyl alcohol,
18h is dried at 60 DEG C, obtains single SnO2Catalyst.
By obtained SnO2Catalyst is enterprising in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Row ICP is tested.
Test result shows, obtained SnO2In catalyst, tin element content is 78.6%.
Comparative example 3：
The preparation method of the copper and tin composite oxide catalyst is same as Example 3, and unique difference is：Step
(1) CuSO dissolved in the aqueous solution4·5H2O quality is 13.40g.
By obtained copper and tin composite oxide catalysts in U.S. Pekin-Elmer inductively coupled plasma atomic emissions
ICP tests are carried out on spectrometer.
Test result shows, SnO in obtained copper and tin composite oxide catalysts2Content is below 0.02%.
Comparative example 4：
The preparation method of the copper and tin composite oxide catalysts is same as Example 1, and unique difference is：Step
(1) CuSO dissolved in the aqueous solution4·5H2O quality is 9.85g.
By obtained copper and tin composite oxide catalysts in U.S. Pekin-Elmer inductively coupled plasma atomic emissions
ICP tests are carried out on spectrometer.
Test result shows, SnO in obtained copper and tin composite oxide catalysts2Content is more than 1%.
Comparative example 5：
(1) at 20 DEG C, 100mL 0.1mol/L sodium hydroxide solution is added to 50mL and is dissolved with 9.20g in advance
CuSO4·5H2O and 0.01g SnCl4·5H2O(mol(Cu):Mol (Sn)=1500:And 0.01g FeCl 1)3·6H2O's
In the aqueous solution, it is stirred until homogeneous, obtains mixed liquor；
(2) by mixed liquor in 0 DEG C of aging 4h；
(3) mixed liquor after aging is transferred in the 200mL autoclave of polytetrafluoroethyllining lining, the water at 130 DEG C
After thermal response 18h, 20 DEG C are naturally cooled to, filtering, gained solid is washed for several times, afterwards repeatedly with deionized water and absolute ethyl alcohol
24h is dried at 60 DEG C, obtains composite oxide catalysts.
By obtained composite oxide catalysts in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrums
ICP tests are carried out on instrument.
Test result shows that CuO content is less than 99.0%, and SnO in obtained composite oxide catalysts2Content
0.02~1%.
Embodiment 8：The evaluation of catalyst
This example is used to illustrate in " direct method " synthesis M2 reactions, is catalyzed made from embodiment 1~7 and comparative example 1~5
The activity of agent, test result are as shown in table 1.
Catalyst performance evaluation is carried out using miniature fixed bed device, reactor inside diameter 20cm, length 50cm, evaluation
Process is as follows：Copper and tin composite oxide catalysts made from 10g Si powder and 0.5g and 0.05g business zinc powder are uniformly mixed
Afterwards, ground and mixed forms contact；During reaction, first using N2Reaction system is purged, then, MeCl gases are switched to, by pre-
Reaction is in contact after heat with contact, reacted product flows out from reactor lower end, is received after condensed pipework condensation using toluene
Collection, unnecessary tail gas after alkali liquor absorption with emptying；Pass through capillary gas chromatography (Agilent after the mixed liquor constant volume of collection
7890A, KB-210 chromatographic column, TCD detectors) carry out quantitative analysis.
The catalyst activity test result table of table 1(1)
Note：(1) reaction condition：Preheating temperature is 350 DEG C, and reaction temperature is 325 DEG C, and reaction pressure is normal pressure, chloromethanes
Flow velocity is 25mL/min, reaction time 24h.
(2)M1：MeSiCl3(Trichloromethyl silane)；M2：Me2SiCl2(dimethyldichlorosilane), M3：Me3SiCl
(tri-methyl-chlorosilane)；M1H：MeHSiCl2(monomethyl silane containing hydrogen)；M2H：Me2HSiCl (dimethyl silane containing hydrogen)；
LBR：Low-boiling-point substance；HBR：High-boiling components；Product distribution is calculated by the percentage of reaction product corresponding area, and silicon conversion calculates public
Formula is as follows：
Wherein, W is the weight of contact.
(3) industrial CuO：Particle diameter after crushing and screening is about 4 μm；Industrial SnO2：Particle diameter is about 4 μm after crushing and screening；Work
Industry CuO+ industry SnO2：By industrial CuO and industrial SnO2Mechanical mixture, based on weight/mass percentage composition, CuO accounts for 99.9%, SnO2Account for
0.1%.
As it can be seen from table 1 when being catalyzed M2 monomer synthetic reactions using industrial CuO, M2 is selectively only 69.0%, Si powder
Conversion ratio is also only 32.8%；Industrial SnO2Catalytically inactive；And by industrial CuO and industrial SnO2After mechanical mixture, catalytic activity
It is obviously improved, M2 selectively rises to 78.9%, Si powder conversion ratios and rises to 43.5%, shows CuO and SnO2Between deposit really
Mutually acting synergistically；Compared with industrial CuO, catalytic performance greatly improves single CuO prepared by comparative example 1 of the present invention, M2 choosings
Selecting property reaches 81.2%, Si powder conversion ratios and reaches 45.5%, it was demonstrated that method provided by the invention has obvious advantage；When using real
When applying copper and tin composite oxide catalysts made from example 1~7, although the constituent content of copper and tin composite oxide catalysts is different,
Catalytic performance slightly has difference, but catalytic activity and selectivity further improve compared with comparative example 1 and 2, and M2 selectivity >=
90.0%, 93.9% is reached as high as, silica flour conversion ratio >=66.0%, reaches as high as 81.1%；And use certain business ternary copper-based
During catalyst monomer synthetic reaction, most important index M2 selectivity is only that 75.5%, Si powder conversion ratios are also only
48.4%, it was demonstrated that copper and tin composite oxide catalysts provided by the invention have excellent catalytic performance.From comparative example 3,4 and 5
In as can be seen that in the copper and tin composite oxide catalysts SnO2Content be less than 0.02% when, catalyst M2 selectivity≤
75.0%, silicon power raw material conversion ratio≤40.0% is not active high；As SnO in copper and tin composite oxide catalysts2Content be more than
When 1%, M2 selectivity≤20.0% of catalyst, silicon power raw material conversion ratio≤10.0%, activity is obvious to be reduced；When copper and tin is compound
CuO content is less than 99.0%, and SnO in oxide catalyst2Content at 0.02~1%, the activity decrease of catalyst
Substantially, M2 selectivity≤40.0%, silicon power raw material conversion ratio≤30.0%.Illustrate that copper and tin composite oxides provided by the invention are urged
CuO and SnO in agent2Content it is optimal.
It is above-mentioned test result indicates that, for M2 monomer synthetic reactions, with industrial catalyst, comparative example 1 and 2 prepare list
One CuO and SnO2And commercial catalysts are compared, the catalyst that method provided by the invention is prepared is in terms of catalytic performance
With significant advantage.This mainly have of both reason, one, laminar catalyst pattern provided by the invention it is homogeneous, distribution is equal
It is even, acted synergistically between component stronger；2nd, laminar catalyst provided by the invention has bigger specific surface area, up to 80~
100m2/ g, the contact probability between catalyst components and silica flour are effectively increased, therefore result in more Cu3Si lives
Property phase, so as to improve M2 selectivity and silica flour conversion ratio.
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can readily occur in, all fall within protection scope of the present invention and it is open within the scope of.
Claims (29)
1. a kind of copper and tin composite oxide catalysts, it is characterised in that the copper and tin composite oxide catalysts are accounted for by each component
Weight/mass percentage composition mainly include following component：
CuO 99.00~99.98%
SnO20.02~1.00%
The weight/mass percentage composition sum of each component is 100%；
Wherein, the SnO2It is dispersed in CuO；
The copper and tin composite oxide catalysts are sheet；
The preparation method of the copper and tin composite oxide catalysts is：Alkali lye and the solution containing copper ion and tin ion are mixed
Close, carry out hydro-thermal reaction after aging in a kettle.
2. copper and tin composite oxide catalysts according to claim 1, it is characterised in that the copper and tin composite oxides are urged
Agent is made up of by the weight/mass percentage composition that each component accounts for following component：
CuO 99.00~99.98%
SnO20.02~1.00%
The weight/mass percentage composition sum of each component is 100%.
3. copper and tin composite oxide catalysts according to claim 1, it is characterised in that the copper and tin composite oxides are urged
The specific surface area of agent is 80~100m2/g。
4. copper and tin composite oxide catalysts according to claim 1, it is characterised in that sheet copper and tin composite oxides are urged
The thickness of agent is 50~60nm.
5. a kind of preparation method of copper and tin composite oxide catalysts according to one of Claims 1 to 4, its feature exist
In the preparation method is：Alkali lye is mixed with the solution containing copper ion and tin ion, enters water-filling after aging in a kettle
Thermal response, obtain copper and tin composite oxide catalysts.
6. preparation method according to claim 5, it is characterised in that, will after methods described also terminates including hydro-thermal reaction
Obtained product carries out separation of solid and liquid, and isolated solid is washed, and dries.
7. preparation method according to claim 5, it is characterised in that copper in the solution containing copper ion and tin ion
The mol ratio of ion and tin ion is 1500~2000:1.
8. preparation method according to claim 5, it is characterised in that copper in the solution containing copper ion and tin ion
The concentration of ion is 0.26~1.56mol/L.
9. preparation method according to claim 5, it is characterised in that the alkali lye contains copper ion and tin ion with described
Solution volume ratio be 1:3~2:1.
10. preparation method according to claim 5, it is characterised in that the concentration of the alkali lye is 0.1~2mol/L.
11. preparation method according to claim 5, it is characterised in that the temperature of the aging is 0~10 DEG C.
12. preparation method according to claim 11, it is characterised in that the time of the aging is 4~24h.
13. preparation method according to claim 11, it is characterised in that the reaction temperature of the hydro-thermal reaction be 100~
180℃。
14. preparation method according to claim 11, it is characterised in that the reaction time of the hydro-thermal reaction be 12~
24h。
15. preparation method according to claim 11, it is characterised in that the reactor is autoclave.
16. preparation method according to claim 15, it is characterised in that the volume of the autoclave be 200~
1000mL。
17. preparation method according to claim 15, it is characterised in that the liner of the autoclave is polytetrafluoroethyl-ne
Alkene.
18. preparation method according to claim 5, it is characterised in that the copper ion source is in soluble copper salt.
19. preparation method according to claim 18, it is characterised in that the soluble copper salt be copper sulphate, copper nitrate,
Any of copper chloride or copper acetate or at least two combination.
20. preparation method according to claim 5, it is characterised in that the tin ion derives from soluble pink salt.
21. preparation method according to claim 20, it is characterised in that the soluble pink salt is nitric acid tin, stannic chloride
Or any of tin acetate or at least two combination.
22. preparation method according to claim 5, it is characterised in that the alkali lye is sodium hydroxide solution, potassium hydroxide
In solution, ammoniacal liquor or urea liquid it is any or at least two mixed liquor.
23. preparation method according to claim 5, it is characterised in that the solvent of the alkali lye contains copper ion with described
Solvent with the solution of tin ion is water and/or ethanol.
24. preparation method according to claim 5, it is characterised in that described be blended at 20~40 DEG C is carried out.
25. preparation method according to claim 24, it is characterised in that be stirred in the mixed process.
26. preparation method according to claim 6, it is characterised in that the temperature of the drying is 60~200 DEG C.
27. preparation method according to claim 26, it is characterised in that the time of the drying is 4~24h.
28. the preparation method according to one of claim 5~27, it is characterised in that the preparation method includes following step
Suddenly：
(1) at 20~40 DEG C, 0.1~2mol/L alkali lye is added in the solution containing copper ion and tin ion, tin from
Son with and copper ion mol ratio be 1500~2000:1, the volume ratio of alkali lye and the solution containing copper ion and tin ion
For 1:3~2:1, obtain mixed liquor；
(2) by mixed liquor in 0~10 DEG C of 4~24h of aging；
(3) mixed liquor after aging is transferred in reactor, hydro-thermal reaction 12~24h, Zhi Hougu is carried out at 100~180 DEG C
Liquid separates, and the washing of gained solid, dries, obtains copper and tin composite oxide catalysts.
29. the purposes of the copper and tin composite oxide catalysts according to one of Claims 1 to 4, it is used for organic silicon monomer
In synthetic reaction, promote the selectivity synthesis of dimethyldichlorosilane.
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